Or x or

ABSTRACT

2. A PHOTOSENSITIVE ELEMENT COMPRISING A SUPPORT CONTAINING A COMPOSITION COMPRISING A. AN ESSENTIALLY COLORLESS, OXIDIZABLE, NITROGEN-CONTAINING, ORGANIC COLOR GENERATOR, WHICH WHEN CONTAINED IN SAID COMPOSITION, IS STABLE TO OXIDATION BY ATMOSPHERIC OXYGEN UNDER NORMAL ROOM AND STORAGE CONDITIONS BUT WHICH IS OXIDIZABLE TO A COLORED MATERIAL AND B. A PHOTO-OXIDANT WHICH IS CAPABLE OF OXIDIZING SAID COLOR GENERATOR TO A COLORED MATERIAL WHEN SUBJECTED TO ACTINIC RADIATION, SAID PHOTO-OXIDANT HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF:   R-O-N(+)&lt;(-Z-)(-R1) X(-) AND R-O-N&lt;(-Z)(-R8)   WHEREIN: R1 IS SELECTED FROM THE GROUP CONSISTING OF: A. A METHINE LINKAGE TERMINATED BY A HETEROCYLIC NUCLEUS OF THE TYPE CONTAINED IN CYANINE DYES, (B. AN ALKYL RADICAL,) B. (C.) AN ANILINOVINYL RADICAL, (D. A HYDROGEN ATOM, E. AN ARYL RADICAL, F. AN ALDEHYDE GROUP,) AND C. (G.) A STYRYL RADICAL; R8 IS SELECTED FROM THE GROUP CONSISTING OF: A. A METHINE LINKAGE TERMINATED BY A HETEROCYCLIC NUCLEUS OF THE TYPE CONTAINED IN MEROCYANINE DYES AND B. AN ALLYLIDENE RADICAL SELECTED FROM THE GROUP CONSISTING OF A CYANOALLYLIDENE RADICAL, AN ALKYLCARBOXYALLYLIDENE RADICAL AND AN ALKYLSULFONYLALLYLIDENE RADICAL; (R) R1 IS SELECTED FROM THE GROUP CONSISTING OF: A. AN ALKYL RADICAL AND B. AN ACYL RADICAL; (X) X- IS AN ACID ANION, AND Z REPRESENTS THE ATOMS NECESSARY TO COMPLETE A FIVE- TO SIX-MEMBERED HETEROCYCLIC NUCLEUS.

United States Patent Oflice Re. 28,240 Retissued Nov. 12, 1974 28,240PHOTOSENSITIVE ELEMENTS CONTAINING PI IOTOOXIDANTS CONTAINING HETERO-CYCLIC NITROGEN ATOM SUBSTITUTED BY AN ALKOXY R AN ACYLOXY GROUP PhilipW. Jenkins, Rochester, N.Y., assignor to Eastman Kodak Company,Rochester, N.Y.

No Drawing. Original No. 3,615,568, dated Oct. 26, 1971,

Ser. No. 859,205, Sept. 18, 1969. Application for reissue Sept. 10,1973, Ser. No. 396,290

Int. Cl. G03c N40, N64 U.S. Cl. 96-90 R Claims Matter enclosed in heavybrackets [1 appears in the original patent but forms no part of thisreissue specification; matter printed in italics indicates the additionsmade by reissue.

ABSTRACT OF THE DISCLOSURE Novel photosensitive elements andcompositions are described. The compositions contain (a) a colorlessoxidizable nitrogen-containing organic color generator and (b) aphotooxidant containing a heterocyclic nitrogen atom which issubstituted by an alkoxy or an acyloxy group. When the photooxidant isexposed to actinic radiation, it causes the oxidation of the colorgenerator to a colored material.

This invention relates to novel photosensitive elements which form anintense color when exposed to actinic radiation and also to novelprocesses utilizing these elements as well as to novel photosensitivecompositions.

The formation of images utilizing dye printout techniques has recentlyreceived considerable attention. Processes have been described whereinvarious leuco compounds have been oxidized to the corresponding leucodyes utilizing organic polyhalogen compounds or oxidizing agents (Phot.Sci. Eng, 598-103 (1961); US. Pat. No. 3,042,515). In a typical processof this type, a mixture of diphenylmethane and carbon tetrabromide isexposed to a pattern of ultraviolet radiation. The radiation causes thehalohydrocarbon to decompose. The decomposition products oxidize thediphenylmethane to the corresponding blue dye.

While the above-described system is very practical, it does have severaldisadvantages. The use of halohydrocarbons as the photo-oxidant isundesirable since these materials generally do not have panchromaticsensitivity but instead are only sensitive in the ultraviolet and nearultraviolet regions. Furthermore, these materials have poor film shelflife because of their volatility and/or thermal instability. Also, theyare not readily removable for purposes of image fixation.

It is, therefore, an object of this invention to provide novelphotosensitive compositions.

It is a further object of this invention to provide novel elementscontaining these compositions.

It is a further object of this invention to provide a novel processutilizing these elements.

These and other objects are accomplished with photosensitive elementscontaining a composition having (a) an essentially colorless oxidizablenitrogen-containing organic color generator which is stable to oxidationby atmospheric oxygen under normal room and storage conditions, butwhich is oxidizable to a colored material and (b) a photo-oxidantcontaining a heterocyclic nitrogen atom which is substituted by eitheran alkoxy group or an acyloxy group. When this element is struck byactinic radiation (e.g., visible, infrared, ultraviolet, X-ray, etc.,including an electron beam), the photo-oxidant decomposes to produce anoxidizing agent. The oxidizing agent causes oxidation of the colorgenerator which results in this materials transposition from anessentially colorless condition to a condition of high coloration. Theparticular color obtained is dependent upon the nature of the colorgenerator, but practically any color can be obtained using variouscombinations of color generators.

The properties of the photo-oxidant are such that it is easilystabilized against further decomposition by treating it with an acid ora base at a pH that has no efl'ect on the photo-oxidant.

An advantage of the present invention over prior art systems is that thevarious photo-oxidants are responsive to various forms of actinicradiation as explained previously, whereas prior art systems aregenerally limited to response to radiation in the ultraviolet region.Also, the photo-oxidants of this invention are less volatile than thehalohydrocarbons which are conventionally used as photooxidants. Assuch, the film shelf life is improved. A third advantage is that thephotooxidants used in the present invention are easily deactivated bytreatment with either an acid or base depending on the particularphoto-oxidant used.

The novel compositions and elements of this invention have several uses.One of these uses is in printing where a paper is impregnated with thephotosensitive composition and then imagewise exposed to the patternbeing printed. Other uses include pattern layout for metal working,preparation of blueprints in a diazo process and in microfilming. Thematerials of the invention are especially useful in microfilming sincethe resolution obtainable is very good. High resolutions are obtainablesince the active particles are of molecular size (i.e., 135 A. for colorgenerator molecules vs. 500 A. for very fine-grain silver halideparticles).

Many types of organic compounds function as organic color generatorsaccording to the invention. All are characterized as being essentiallycolorless, containing nitrogen, being stable to oxidation under normalstorage conditions in the photosensitive composition and being capableof producing a color in a photo-oxidative process in the presence of aphoto-oxidant. The process may be a simple oxidation of the colorlesscompound to a colored species. The oxidation may initially produce areactive intermediate which then undergoes a further reaction with asecond component of the color generator to produce the final coloredspecies. In some cases, the reactive intermediate combines with thephoto-oxidant to produce a color species. Mixtures of color generatorsmay be used. These color generation processes, and the compounds whichare adapted for them, are discussed in detail below.

Useful color generators of this invention include the following:

I. Leuco form of dyes-One type of color generator which may form part ofthe light-sensitive composition is the reduced form of the dye having,in most cases, one or two hydrogen atoms, the removal of which togetherwith one or two electrons produces a dye. Since leuco form of the dye isessentially colorless, or in some instances it may be of a differentcolor or of a less intense shade than the parent dye, it provides ameans of producing an image when the leuco form is oxidized to the dye.This oxidation is accomplished by subjecting an intimate admixture ofthe organic color generator and a photo-oxidant discussed below to apattern of actinic radiation. The result is the removal of one or tworeadily removable hydrogen atoms, depending on the structure of theleuco form of the particular dye chosen, with the production of acolored image against a background of unradiated and, therefore,unchanged material. Representative dyes in the leuco form which areoperative according to the invention include:

a. Aminotriarylmethanes bis(4-amino-2-butylphenyl)(p-dimethylaminophenyl) methane 3 ,6-bis (diethylamino -9-phenylxanthene3,6-bis( diethylam ino -9-o-tolylxanthene3,6-bis(dimethylamino)-9-(o-ch1orophenyl)xanthene 3 ,6-bis dimethylamino-9-ethylxanthene 3 ,6-bis dimethylamino -9- (o-methoxycarbonylphenyl)xanthene 3,6-bis dimethylamino -9-methylxanthene c. Aminothioxanthenes3,6-bis(diethylamino) -9- (o-ethoxycarbonylphenyl) thioxanthene3,6-bis(dimethylamino)-9- (o-methoxycarbonylphenyl) thioxanthene3,6-bis(dimethylamino)thioxanthene 3,6-diar1ilino-9-(o-ethoxycarbonylphenyl thioxanthene d.Amino-9,IO-dihydroacridines 3 ,6-bis benzylamino -9,l-dihydro-9-methylacridine 3,6-bis(diethylamino -9-hexyl-9,IO-dihydroacridine 3 ,6-bis diethylarnino -9, lO-dihydro-9-methylacridine3,6-bis(diethylamino)-9,10-dihydro-9-phenylacridine 36-diamino-9-hexyl-9, l O-dihydroacridine3,6-diamino-9,10-dihydro-9-methylacridine3,6-diamino-9,lO-dihydro-9-phenylacridine3,6-bis(dimethylamino)-9-hexyl-9, IO-dihydroacridine3,6-bis(dimethylamino)-9,10-dihydro-9-methylacridine e.Aminophenoxazines 3,7-bis (diethylamino phenoxazine-dimethylamino-benzo[a]phenoxazine f. Aminophenothiazines 3,7-bis(benzylamino phenothiazine g. Aminodihydrophenazines 3,7-bisbenzylethylamino) -5, lfl-dihydro-S-phenylphenazine 3,7-bis(diethylamino --hexy1-5, IO-dihydrophenazine 3 ,7-bis dihexylamino -S lO-dihydrophenazine 3 ,7-bis(dimethylamino)-5-(p-chlorophenyl)-5,10-

dihydrophenazine 3 ,7-diamino-5- (o-chlorophenyl -5, 1O-dihydrophenazine 3 ,7-diamino-5, 1 fl dihydrophenazine 3,7-diamino-5,1 O-dihydro-S-methylphenazine 3 ,7-diamino-5-hexyl-5, lO-dihydrophenazine 3 ,7-bis (dimethylamino -5 1 O-dihydrophenazine 3,7-bis(dimethylamino)-5,10-dihydro-S-phenylphenazine3,7-bis(dimethylarnino)-5,10-dihydro-S-methylphenazine h.Aminodiphenylmethanes 1,4-bis bis-pdiethylaminophenyl methyl piperazinebis p-diethylaminophenyl anilinomethane bis p-diethylaminophenyl)l-benzotriazolylmethane bis( p-diethylaminophenyl-2-benzotriazolylmethane bis (p-diethylaminophenyl)p-chloroanilino)methane bis(p-diethylaminophenyl)(2,4-dichloroanilino)methane bis(p-diethylaminophenyl)(methylamino)methane bis(p-diethylaminophenyl) (octadecylamino methanebis( pdimethylaminophenyl) aminomethane bis(p-dimethylaminophenylanilinomethane 1, l-bis (dimethylaminophenyl)ethane1,1-bis(dimethylaminophenyl)heptane bis(4methylamino-m-t0lyl)aminoethanei. Leuco indamines 4-amino-4'-dimethylaminodiphenylaminepp-dimethylaminoanilino phenol j. Aminohydrocinnamic acids(cyanoethanes, leuco methines) 4-amino-a,,6-dicyanohydrocinnamic acid,methyl ester 4-anilino-a,fidicyanohydrocinnamic acid, methyl ester 4-(p-chloroanilino) -a,p-dicyanohydrocinnamic acid,

methyl ester a-cyano-4-dimethylaminohydrocinnamamide k. Hydrazines 1-(p-diethylaminophenyl)-2-( 2-pyridyl)hydrazinel-(pdimethylaminophenyl)-2(2-pyridyl)hydrazine1-(3-methyl-2-benzothiazolyl)-2-(4-hydroxy-l-naphthyl) hydrazinel-(2-naphthyl -2-phenylhydrazine 1-p-nitrophenyl-2-pheny1hydrazine1-(l,3,3-trimethyl-2-indolinyl)-2-(3-N-phenylcarbamoyl-4-hydr0Xy-1-naphthyl hydrazine l. Leuco indigoid dyes m.Amino-2,3-dihydroanthraquinones 1,4-dianilino-2,3-dihydroanthraquinonel,4-bis(ethylamino)-2,3-dihydroanthraquinone n. PhenethylanilinesN-(2-cyanoethyl -p-phenethylaniline N,N-diethyl-p-phenylethylani]incN,N-dimethyl-p- 2-( l-naphthyl ethyl] aniline 11. Acyl derivatives ofleuco dyes which contain a basic NH groupSuitable compounds which have abasic NH group and which form amides when acylatcd includedihydrophenazines, phenothiazines and phenoxazines. Typical compoundswithin this class include:

l0-acetyl-3,7-bis(dimethylamino)-phenothiazine10-(p-chlorobenzoyl)-3,7-bis(diethylamino)- phenothiazine5,10-dihydro-IO-(p-nitrobenzoyl)-5-phenyl-3,7-

bis-(phenylethylamino)phenazine10-(p-benzoyl)-3,7-bis(naphthylmethylamino) phenoxazine III. Leucolikecompound having no oxidizable hydrogen atom but which are oxidizable toa colored compound-Typical compounds within this class include:

tris( p-dirnethylaminophenyl benzylthiomethane1tris(p-diethylaminophenyl)methyl-2-phenylhydrazinetris(4-diethylamino-o-tolyl)ethoxycarbonylmethanebis(4-dipropylamino-o-tolyl) (o-fluorophenyl)butoxycarbonylmethane bis[tris (4-diethylamino-o-tolyl methyl] -disulfide IV. Organic aminesoxidizable to a colored species such as those described in US. Pat. Nos.3,042,515 and 3,042,- 517. Typical compounds of this type include:

4,4'-ethylenedianiline diphenylamine N,N-(dimethylaniline4,4'-methylenedianiline triphenylamine N-vinylcarbazole Thephoto-oxidizers described herein are inert until struck by actinicradiation such as visible, ultraviolet, infrared, X-ray electron beams,etc. Various photo-oxidizers have different peak sensitivitiesthroughout the spectrum depending on the structure of the compound. Assuch, the specific photo-oxidizers selected is dependent on the natureof the actinic radiation. When exposed to such radiation, thephoto-oxidizer produces an oxidizing agent which oxidizes the colorgenerator to a colored form. Typical photo-oxidizers of this inventionhave one of the general formulas:

wherein R can be any of the following:

a. a methine linkage terminated by a heterocyclic nucleus of the typecontained in cyanine dyes, e.g., those set forth in Mees and James, TheTheory of the Photographic Process," Macmillan, 3rd ed., pp. 198-232;the methine linkage can be substituted or unsubstituted, CH a 'C(C6H5):!

b. an alkyl radical preferably containing one to eight carbon atomsincluding a substituted alkyl radical;

c. an aryl radical including a substituted aryl radical such as a phenylradical, a naphthyl radical, a tolyl radical, etc.;

d. a hydrogen atom;

e. an acyl radical having the formula 3 -C-R9 wherein R is hydrogen oran alkyl group preferably having one to eight carbon atoms;

f. an anilinovinyl radical such as a radical having the formula whereinR is hydrogen, acyl or alkyl; or a styryl radical including substitutedstyryl radicals,

wherein R is hydrogen, alkyl, aryl, amino, including dialkylamino suchas dimethylamino;

R can be either of the following:

a. an alkyl radical preferably having one to eight carbon atoms such asmethyl, propyl, ethyl, butyl, etc., including a substituted alkylradical such as sulfoalkyl, e.g., -(CH SO an aralkyl, e.g., benzyl orpyridinatooxyalkyl salt. e.g (CH -O-Y wherein Y is substituted orunsubstituted pyridinium salt; or etc.,

b. an acyl radical, e.g.,

wherein R is an alkyl radical preferably having one to eight carbonatoms or aryl radical, e.g., methyl, ethyl, propyl, butyl, phenyl,naphthyl, etc.

Q Q and Q each represent the nonmetallic atoms necessary to complete asensitizing or desensitizing nucleus containing five or six atoms in theheterocyclic ring, which nucleus can contain at least one additionalheteroatom such as oxygen, sulfur, selenium or nitrogen, i.e., a nucleusof the type used in the production of cyanine dyes, such as thefollowing representative nuclei: a thiazole nucleus, e.g., thiazole,4-rnethylthiazole, 3 ethylthiazole, 4-phenylthiazole, S-methylthiazole,5 phenyl thiazole, 4,5-dimethylthiaz0le, 4,5-diphenylthiazole, 4-(2-thienyUthiazole, benzothiazole, 4-chlorobenzothiazole, 4- orS-nitrobenzothiazole, S-chlorobenzothiazole, 6-chlorobenzothiazole,7-chlorobenzothiazole, 4 methylbenzothiazole, S-methylbenzothiazole, 6methylbenzothiazole, fi-nitrobenzothiazole, S-bromobenzothiazole, 6bromobenzothiazole, 5-chloro-6-nitrobenzothiazole, 4phenylbenziothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole,fi-methoxybenzothiazole, 5 iodobenzothiazole, -iodobenzothiazole, 4ethoxybenzothiazole, 5 ethoxybenzothiazole, a tetrahydrobenzothiazolenucleus, 5,6-dimethoxybenzothiazole, 5,6-methylenedioxybenzothiazole,5-hydroxybenzothiazole, G-hydroxybenzothiazole, a-naphthothiazole,B-naphthothiazole, p143 naphthothiazole, 5-metboxy-[3,fl-naphthothiazole, S-ethoxy ,5 naphthothiazole,8-methoxy-a-naphthothiazole, 7 methoxy-u-naphthothiazole, 4methoxythianaphtheno-7',6', t,5-thiazole, nitro group substitutednaphthothiazoles, etc.; an oxazole nucleus, e.g., 4-methyloxazole,4-nitro-oxazole, S-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole,4 ethyloxazolc, 4,5 dimethyloxazole, 5 phenyloxazole, benzfour carbonatoms), e.g., methyl, ethyl, propyl, isopropyl, butyl, decyl, dodecyl,etc., or an aryl group, e.g., phenyl, tolyl, naphthyl, methoxyphenyl,chlorophenyl, nitrophenyl, etc.;

X represents an acid anion, e.g., chloride, bromide, iodide,perchlorate, tetrafluoroborate, sulfamate, thiocyanate,p'toluenesulfonate, methyl sulfate, etc.;

G represents an anilino radical or an aryl radical, e.g., phenyl,naphthyl, dialkylaminophenyl, tolyl, chlorophenyl, nitrophenyl,anilinovinyl, etc.;

R is an alkyleneoxy radical having one to eight carbon atoms in thealkylene chain including an alkylenedioxy radical and anarylenebisalkoxy radical e.g., ethyleneoxy, trimethyleneoxy,tetrarnethyleneoxy, propylideneoxy, ethylenedioxy, phenylenebisethoxy,etc.;

R represents either (1) an alkyl radical including a substituted alkyl(preferably a lower alkyl having one to four carbon atoms) e.g., methyl,ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl, dodecyl,aralkyl such as benzyl, sulfoalkyl such as B-sulfoethyl, w-sulfobutyl,w-sulfopropyl, or (2) an acyl radical, e.g.,

its.

wherein R is an alkyl including a substituted alkyl or an aryl radicalsuch as methyl, phenyl, naphthyl, propyl, benzyl, etc.

In the above formulas Q preferably completes a pyridine, an indole or aquinoline nucleus.

Typical photo-oxidants included in the scope of this invention are thefollowing:

1. 3-ethyl-l-methoxyoxa-2-pyridocarbocyanine perchlorate 2. 1' ethoxy 3ethyloxa-2'-pyridocarbocyanine tetrafiuoroborate 3' ethyl 1methoxy-Z-pyridothiacyanine iodide 1-ethoxy-3'-ethyl-2-pyridothiacyaninetetrafluoroborate 1-benzyloxy-3-ethyl-2-pyridothiacyanine iodide3'-ethyl-1-methoxy-2pyridothiacarbocyanine iodide1-etboxy-3'-ethyl-2-pyridothiacarbocyanine tetrafluoroborate anhydro 3ethyl 1 (3-sulfopropoxy)-2 pyridothiacarbocyanine hydroxide 9.l-benzyloxy 3' ethyl 2 pyridothiacarbocyanine perchlorate 10. 3'-ethyl 1methoxy-2-pyridothiacarbocyanine perchlorate 11. 1'-methoxy 1,3,3trimethylindo-2'-pyridocarbocyanine pictrate 12. 3'-ethyl 1methoxy-4,5-benzo-2-pyridothiacarbocyanine perchlorate 13. l ethoxy 3'ethyl-4',5'-benzo-Z-pyridnthiacarbocyanine tetrafiuoroborate 14. 1'ethoxy 3 ethyloxa-Z'-carbocyanine tetrafiuoroborate 15.1'-ethoxy-3-ethylthia-2'-cyanine tetrafiuoroborate 16. 1' ethoxy 3ethylthia-2'-carbocyanine tetrafiuoroborate 17. l ethoxy 3ethylthia-2'-dicarbocyanine tetrafiuoroborate l8. 1 methoxy 3methyl-2-pyridothiazolinocarbocyanine perchlorate 19.3'-ethyl-1-methoxy-4-pyridothiacyanine perchlorate 20. 3 ethyl 1methoxy-4-pyridothiacarbocyanine perchlorate 21. 1' ethoxy 3ethyl-4,5-benzothia-2'-carbocyanine tetrafluoroborate 22. 2 Banilinovinyl-l-methoxypyridinium p-toluenesulfonate 23. 1 ethyl 1'methoxy-4,5-benzothia-4'-carbocyanine perchlorate 24. 1 methoxy 2methylpyridinium p-toluenesulfonate 25. l methoxy 4 methylpyridiniump-toluenesulfonate 26. anhydro 2 methyl-1-(3-sulfopropoxy)pyridiniumhydroxide 27. l-ethoxy-Z-methylpyridinium tetrafiuoroborate 28.l-benzyloxy-Z-methylpyridinium bromide 29. 1-ethoxy-2-methylquinoliniumtetrafluoroborate 30. 1,1'-ethylencdioxybispyridinium dibromide 31.1,1-trimethylenedioxybispyridinium dibromide 32. 1,1tctramethylenedioxybifl2-methylpyridinium)dibromide 33. 1,1tetramethylcnedioxybis(4-methylpyridinium)dibromide 34.1,1-tetramethylenedioxybispyridinium dibromide 35.1,1'-pentamethylenedioxybispyridinium dibromide 36. 1 acetoxy 2 (4dimethylaminostyryl)pyridinium perchlorate 37. l benzoyloxy 2(4-dimethylaminostyryl)pyridinium perchlorate 38. 1,3diethyl-S-ltt-methoxy-2(lH)-pyridylidene)ethylidene]-2-thiobarbituricacid 39. 3 ethyl 5-[(l-methoxy-2(1H)-pyridylidene)ethylidenelrhodanine40. 1,3 diethyl 5 [(1-methoXy-2(1H)-pyridylidene) ethylidenel-barbituricacid 41. 2- 3,3-dicyanoalky1idene)-1-methoxy-1,2-dihydropyridine 42. 2[(1 methoxy-2(1H)-pyridylidene)-ethylidene}benzo[b'|-thiophen-3(211)-one-L1-dioxide 43. 3 cyano 5[t1-methoxy2(1H)-pyridylidene)ethylidene |-4-phenyl2(5H -furanone 44.N-ethoxy-2-picolinium iodide 45. N-ethoxy2-picoliniumhexafluorophosphate 46. N-methoxy 2 anilinovinylpyridiniumparatoluenesulfonate Photosenstive elements of this invention can beprepared from the color generators and photo-oxidizers of this inventionin the usual manner, i.e., by blending a dispersion or solution of thecolor generator and photooxidizer together with a binder, when necessaryor desirable, and coating, impregnating or forming a self-supportinglayer from the photosensitive composition.

Binders which may optionally be added to the composition are inertmaterials that serve to adhere the color generator-photo-oxidizermixture to a substrate. The binder may also serve to thicken thesolution of the composition should this be desirable for specificapplications. Representative binders that are suitable for use in thepresent composition include: styrene-butadiene copolymers; siliconeresins; styrene-alkyd resins; silicone-alkyd resins; soya-alkyd resins;poly(vinylchloride); poly(vinylidene chloride); vinylidenechlorideacrylonitrile copolymers; poly(vinyl acetate); vinylacetatevinyl chloride copolymers; poly(vinyl acetals), such aspo1y(vinyl butyral); polyacrylic and methacrylic esters, such as poly-(methylmethacrylate), poly(n butylmethacrylate), poly-(isobutylmethacrylate), etc.; polystyrene, nitrated polystyrene;polymethylstyrene; isobutylene polymers; polyesters, such aspoly-(ethylenealkaryloxyalkylene terephthalate); phenolformaldehyderesins; ketone resins; polyamides; polycarbonates; polythiocarbonates;poly(ethyleneglycol co bis hydroxyethoxyphenyl propane terephthalate);copolymers of vinyl haloarylates and vinyl acetate such as poly(vinylm-bromobenzoate-covinylacetate); ethyl cellulose, poly(vinyl alcohol),cellulose acetate, cellulose nitrate, chorinated rubber, gelatin, etc.Methods of making resins of this type have been described in the priorart, for example, styrene-alkyd resins can be prepared according to themethod described in U.S. Pat. Nos. 2,361,019 and 2,258,423. Suitableresins of the type contemplated for use are sold under such tradenamesas Vitel PEAOI, Cymac, Piccopale 100, Saran F220, Lexan and Lexan 145.Other types of binders which can be used include such materials asparafiin, mineral waxes, etc.

The substrates are materials which bear the light-sensitive,image-forming compositions as a coating or impregnant. These materialsinclude paper ranging from tissue paper to heavy cardboard; films ofplastics and polymeric materials such as regenerated cellulose,cellulose acetate, cellulose nitrate, polyester of glycol andterephthalic acid, vinyl polymers and copolymers, polyethylene,polyvinylacetate, polymethyl methacrylate, polystyrene,polyvinylchloride; textile fabrics; glass; wood and metals. Opaque aswell as transparent substrates can be used. Substrates in which thephotosensitive components are dissolved or which bear the photosensitivecomponents as a coating on the reverse side of the substrate, i.e., onthe side away from the radiation source used for image formation, mustbe transparent not only in the visible region but to any form ofradiation employed. The substrates should be inert to the photosensitivematerials.

Solvents which are inert toward the color generator, the binder and thephoto-oxidizer are usually employed to dissolve these comronents andthereby mix them together and to provide a fluid medium for a convenientand ready application of the photosensitive composition to substrates.Among the solvents which may be employed in preparing the compositionsof this invention are amides such as formamide, N,N-dimethylformamide,N,N dimethylacetamide, hexanimide, styramide; alcohols such as methanol,ethanol, l-propanol, Z-propanol. butanol; glycols such asethyleneglycol, polyethyleneglycol, etc.; ketones such as acetone,2-butanone, etc.; esters such as ethylacetate, ethylbenzoate, etc.;ethers such as tetrahydrofuran, dioxane, etc.; chlorinated aliphatichydrocarbons such as methylene chloride, ethylene chloride, etc.;aromatic hydrocarbons such as benzene, toluene, etc.; and other commonsolvents such as dimethylsulfoxide, odichlorobenzene,dicyanocyclobutane, l-methyl-Z-oxohexamethylenimine, and variousmixtures of the solvents, transparent not only in the visible region butto any form of radiation employed. The substrates should be inert to thephotosensitive materials.

Solvents which are inert toward the color generator, the binder and thephoto-oxidizer are usually employed to dissolve these components andthereby mix them together and to provide a fluid medium for a convenientand ready application of the photosensitive composition to substrates.Among the solvents which may be employed in preparing the compositionsof this invention are amides such as formamide, N,N-dirnethylformamide,N,N-dimethylacetamide, hexanimide, styramide; alcohols such as methanol,ethanol, l-propanol, 2-propanol, butanol; glycols such asethyleneglycol, polyethyleneglycol, etc.; ketones such as acetone,Z-butanone, etc.; esters such as ethylacetate, ethylbenzoate, etc.,ethers such as tetrahydrofuran, dioxane, etc.; chlorinated aliphatichydrocarbons such as methylene chloride, ethylene chloride, etc.;aromatic hydrocarbons such as benzene, toluene, etc.; and other commonsolvents such as dimethylsulfoxide, o-dichlorobenzene,dicyanocyclobutane, 1-methyl-2-oxohexamethylenimine, and variousmixtures of the solvents.

In preparing the compositions disclosed herein useful results areobtained when the color generator and photooxidizer are mixed in moleratios within the range from about :1 to about 1:10. The preferred ratiorange is 2:1 to 1:2. The binder, when used, is employed in an amountvarying from about 0.5 part to 10 parts by weight per part of combinedweight of color generator and photooxidizer. The combined weight ofcolor generator and photo-oxidizer in the composition ranges from about1 weight percent to about 99 weight. A preferred weight range is fromabout 2 weight percent to about 60 weight percent.

In preparing the compositions disclosed herein useful results areobtained when the color generator and photooxidizer are mixed in moleratios within the range from about 10:1 to about 1:10. The preferredratio range is 2:1 to 1:2. The binder, when used, is employed in anamount varying from about 0.5 part to 10 parts by weight per part ofcombined weight of color generator and photo-oxidizer. The combinedweight of color generator and photo-oxidizer in the composition rangesfrom about 1 Weight percent to about 99 Weight A preferred weight rangeis from about 2 weight percent to about 60 weight percent.

When the compositions are coated, a wet thickness of about 0.001 inch toabout 0.01 inch is utilized, the preferred range being from about 0.002inch to about 0.006 inch. When the composition is impregnated into asupport, suitable amounts of color generator and photo-oxidizer rangefrom about 0.01 mg./in. to about 5.0 mg./ in. of each.

In applying the composition to a supporting substrate, the compositioncan be sprayed, brushed, applied by a roller or immersion coater, flowedover the surface, picked up by immersion, impregnated or spread by othermeans. Elements thus formed are dried at room temperature, under vacuumor at elevated temperature.

The elements are then exposed to a pattern of actinic radiation and theimage is formed directly on the support. The exposure can be by contactprinting techniques, by lens projection, by reflex, by bireflex, from animagebearing original or any other known technique. Fixing isaccompilshed merely by destroying residual photo-oxidant by treating itwith alkaline or acid depending on the nature of the photo-oxidant or bythe use of a reducing agent to destroy the oxidizing agent present inunexposed areas.

The following examples are included for a further understanding of theinvention.

EXAMPLE 1 A composition in the form of a dope consisting of thefollowing materials is coated at a wet thickness of 0.003 inch on apaper support.

G. Color generator 0.1 Photo-oxidant 0.25 Binder[poly(vinyl acetate)]2.0 Methylene chloride 18.0

The resultant colorless coating is dried at 40 C. for 30 minutes andexposed for 30 seconds behind a halftone positive with a photofioodlamp. The color generator used, photo-oxidant used, and color of the dyeimage are set forth in the following table I.

Example 1 is repeated except that the light source used is a mercury arc(Filmsort 086). Similar results are obtained.

EXAMPLE 3 A composition in the form of a dope consisting of thefollowing materials is coated at a wet thickness of 0.003 inch on apaper support and dried:

Color generator 0.02 Photo-oxidant(N-ethoxy 2-picoliniumhexafluorophosphate 0.04

Binder [poly(vinylbutyral)] 2.0

Methylene chloride 18.0

The element containing a colorless coating is exposed in an imagewisemanner to radiation from a mercury arc. The color-generator used and thecolor of the dye image are set forth in the following table II.

p-(2.2-Dicyanoethyl-N,N-dimethylaniline Yellow. p-( l,2,2 Tricyanoethyl)N,N dimethylaniline Orange. p-Phenylenediamine Gray. Tris(4 diethylamino(4 tolyl)methane trihydro chloride Blue.

EXAMPLE 4 Example 3 is repeated except that the photo-oxidant employedis N-methoxy-Z-anilinovinylpyridinium paratoluenesulfonate. Similarresults are obtained. When the photooxidant is omitted, the coatingremains colorless.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

I claim:

[1. A photosensitive element comprising a support containing acomposition comprising a. an essentially colorless, oxidizable, nitrogencontaining, organic color generator, which when contained in saidcomposition, is stable to oxidation by atmospheric oxygen under normalroom and storage conditions but which is oxidizable to a coloredmaterial and b. a photo-oxidant containing a heterocyclic nitrogen atomwhich is substituted by a member selected from the group consisting ofan alkoxy group and an acyloxy group, said photo-oxidant being capableof oxidizing said color generator to a colored material when subjectedto actinic radiation] 2. A photosensitive element comprising a supportcontaining a composition comprising a. an essentially colorless,oxidizable, nitrogen-containing, organic color generator, which whencontained in said composition, is stable to oxidation by atmosphericoxygen under normal room and storage conditions but which is oxidizableto a colored material and b. a photo-oxidant which is capable ofoxidizing said color generator to a colored material when subjected toactinic radiation, said photo-oxidant having a formula selected from thegroup consisting of:

wherein:

R is selected from the group consisting of:

a. a methine linkage terminated by a heterocyclic nucleus of the typecontained in cyanine dyes,

[b. an alkyl radical] b. [e] an anilinovinyl radical,

[d. a hydrogen atom,

e. an aryl radical,

f. an aldehyde grouPJ and c. [g.] a styryl radical;

R is selected from the group consisting of:

a. a methine linkage terminated by a heterocyclic nucleus of the typecontained in merocyanine dyes and b. an allylidene radical selected fromthe group consisting of a cyanoallylidene radical, analkylcarboxyallylidene radical and an alkylsulfonylallylidene radical;

[R] R is selected from the group consisting of:

a. an alltyl radical and b. an acyl radical;

[X] X- is an acid anion, and, Z represents the atoms necessary tocomplete a fiveto six-membered heterocyclic nucleus.

[3. The element as defined in claim 2 wherein Z represents the atomsnecessary to complete a member selected from the group consisting of apyridine nucleus and a quinoline nucleus] 4. The element as defined inclaim 2 wherein R is a methine linkage terminated by fiveto six-memberedheterocyclic nucleus.

5. The element as defined in claim 2 wherein said composition contains apolymeric binder for said organic color generator and saidphoto-oxidant.

6. The element as defined in claim 2 wherein said composition is imbibedinto the support.

7. The element as defined in claim 2 wherein said composition is coatedon the support.

8. The element as defined in claim 2 wherein said component (a) isselected from the group consisting of (1) a leuco dye; (2) an N-acylderivative of a leuco dye; (3) a substituted triarylmethane wherein thesingle remaining methane bond is substituted with benzylthio,Z-phenylhydrazino, alkoxycarbonyl or disulfide; and (4) an organicamine.

9. The element as defined in claim 2 wherein said component (b) isselected from the group consisting of:

Q Q and Q [Q each represent the nonmetallic atoms necessary to completea fiveto six-membered heterocyclic nucleus;

11 is a positive integer of from 1 to 4;

m is a positive integer of from 1 to 3;

[R is an alkyleneoxy radical having one to eight carbon atoms in thealkylene chain;]

g is a positive integer from 1 t0 2;

[X X is an acid anion;

L is a methine linkage;

[R] R is selected from the group consisting of an alkyl radical and anacyl radical;

R [and R are each] is selected from the group consisting of an arylradical, a hydrogen atom and an alkyl radical;

R is selected from the group consisting of an alkyl radical, an alkenylradical, an aryl radical and an alkoxy radical;

G is selected from the group consisting of an anilinovinyl radical andan aryl radical; and

R and R are each a cyano radical.

[10. A photosensitive element comprising a support having coated thereona composition comprising a. from about 0.1 to about percent by weight oftris-(pdimethylaminophenyl)methane as a color generator,

b. from about 0.1 to about 10 percent by weight of N-ethoxy-Z-picoliniumiodide as a photo-oxidant, and

c. a polymeric binder] [11. A photosensitive element comprising asupport having coated thereon a composition comprising a. from about 0.1to about 10 percent by weight of tris-(p-dimethylaminophenyl)methane asa color generator,

b. from about 0.1 to about 10 percent by weight of N-ethoxy-Z-picoliniumhexafiuorophosphate as a photo-oxidant and c. a polymeric binder] 12. Aphotosensitive element comprising a support having coated thereon acomposition comprising a. from about 0.1 to about 10 percent by weightof tris-(p-dimethylaminophenyl)methane as a color generator,

b. from about 0.1 to about 10 percent by weight of N-methoxy 2anilinovinylpyridinium paratoluenesulfonate as a photo-oxidant and c. apolymeric binder.

[13. A photosensitive composition comprising a. an essentiallycolorless, oxidizable, nitrogen containing, organic color generator,which when contained in said composition, is stable to oxidation byatmospheric oxygen under normal room and storage conditions but which isoxidizable to a colored material and b. a photo-oxidant containing aheterocyclic nitrogen atom which is substituted by a member selectedfrom the group consisting of an alkoxy group and an acyloxy group, saidphoto-oxidant being capable of oxidizing said color generator to acolored material when subjected to actinic radiation] 14. Aphotosensitive composition comprising a. an essentially colorless,oxidizable, nitrogen-containing, organic color generator, which whencontained in said composition, is stable to oxidation by atmosphericoxygen under normal room and storage conditions but which is oxidizableto a colored material and a photo-oxidant which is capable of oxidizingsaid color generator to a colored material when subjected to actinicradiation, said photo-oxidant having a formula selected from the groupconsisting of:

(BR 5R wherein:

b. [c.] an anilinovinyl radical,

[d. a hydrogen atom,

c. an aryl radical,

f. an aldehyde group] and c. [g] a styryl radical;

R; is selected from the group consisting of:

a. a methine linkage terminated by a heterocyclic nucleus of the typecontained in merocyanine dyes and b. an allylidene radical selected fromthe group consisting of a cyanaallylidene radical, analkylcarboxyallylidene radical and an alkylsulfonylallylidene radical;

[R] R is selected from the group consisting of a. an alkyl radical andb. an acyl radical;

X [X] is an acid anion; and, Z represents the atoms necessary tocomplete a fiveto six-membered heterocyclic nucleus.

15. The photosensitive composition as defined in claim 14 wherein Zrepresents the atoms necessary to complete a member selected from thegroup consisting of a pyridine nucleus and a quinoline nucleus.

16. The photosensitive composition as defined in claim 14 wherein R is amethine linkage terminated by a fiveto six-membered heterocyclicnucleus.

17. The photosensitive composition as defined in claim 14 wherein saidcomposition contains a polymeric binder for said organic color generatorand said photo-oxidant.

18. The photosensitive composition as defined in claim 14 wherein saidcomponent (a) is selected from the group consisting of (1) a leuco dye;(2) an N-acyl derivative of a leuco dye; (3) a substitutedtriarylmethane wherein the single remaining methane bond is substitutedwith benzylthio, 2-phenyl-hydrazino, alkoxycarbonyl 0r disulfide; and(4) an organic amine.

19. The photosensitive composition as defined in claim 14 wherein saidcomponent (b) is selected from the group consisting of wherein:

Q Q and Q, [Q] each represent the nonmetallic atoms necessary tocomplete a fiveto siX-membered heterocyclic nucleus;

n is a positive integer from 1 to 4;

m is a positive integer from 1 to 3;

[R is an alkyleneoxy radical having one to eight carbon atoms in thealkylene chain;]

g is a positive integer from 1 to 2;

X is an acid anion;

L is a methine linkage;

[R] R is selected from the group consisting of an alkyl radical and anacyl radical;

R; [and R are each] is selected from the group consisting of an arylradical, a hydrogen atom and an alkyl radical;

R is selected from the group consisting of an alkyl radical, an alkenylradical, an aryl radical and an alkoxy radical;

G is selected from the group consisting of an aminovinyl radical and anaryl radical; and

R and R are each a cyano radical.

20. A process for producing a visible image comprising the steps of A.providing a photosensitive element comprising a support containing acomposition comprising a. an essentially colorless, oxidizable,nitrogencontaining, organic color generator, which when contained insaid composition, is stable to oxidation by atmospheric oxygen undernormal room and storage conditions but which is oxidizable to a coloredmaterial and b. a photo-oxidant containing a heterocyclic nitrogen atomwhich is substituted by a member selected from the group consisting ofan alkoxy group and an acyloxy group, said photo-oxidant being capableof oxidizing said color generator to a colored material when subjectedto actinic radiation, and B. exposing said element to a pattern ofactinic radiation.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

UNITED STATES PATENTS RONALD H. SMITH, Primary Examiner W. H. LOUIE,JR., Assistant Examiner US. Cl. X.R.

Page 1 of pages I UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATEOF CORRECTION PATENT NO. Re. 28,2 LO

DATED Reissued November 12, 197A INVENTOROSQ Philip W. Jenkins It iscertified that error appears in the above-Identified patent and thatsaid Letters Patent are herelg corrected as shown below: Column line 71,that part of formula reading (p-dimethylaminophenyl) should read(p-dimethylaminophenyl)- Column 3, line 6, that part of formula reading(p-methoxyphenyl) should read (P-methoxyphenyl)- line 20, that part offormula reading "(p-aminophenyl)" should read (paminophenyl)- ---5 line25, "(p-diethylaminophenyl)methane" should be on the preceding lineimmediately after methane" and also should read p-diethylaminophenylmethane --5 line 26, that part of formula reading"(pdimethylaminophenyl)" should read (p-dimethylaminophenyl)- line 28,that part of formula reading "(p-methoxyphenyl) should read(p-methoxyphenyl)- line 32, that part of formula reading"(p-diethylaminophenyl)" should read (p-diethylaminophenyl3- line 38,that part of formula reading "ethylaminophenyl should readethylaminophenyl]- --5 line +7, that part of formula reading"(p-diethylaminophenyl)" should read (pethylaminophenyl)- ---5 line 60,that part of formula reading "naphthyl) should read naphthyl)- --5 line62, that part of formula reading "(p-dimethylaminophenyl)" should read(pdimethylaminophenyl) --line 6 that part of formula reading "naphthyl)"should read naphthyl)- --5 line 69, that part of formula reading"(p-diethylaminophenyl) should read p-diethylaminophenyl --line '72,that part of formula reading (p-diethylaminophenyl should read(p-diethylaminophenyl)- line 7 L, that part of formula reading(p-diphenylaminophenyl) should read (p-diphenylaminophenyl) Column L,line 3, that part of formula reading "naphthyl)" should read naphthyl)--5 line Page 2 of t pages 1 UNITED STATES PATENT AND TRADEMARK OFFICECERTIFICATE OF CORRECTION PATENT NO. :Re. 28,2 LO DATED BeissuedNovember 12, 197

INVENTORQE) :Philip W. Jenkins It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below: 5, that part of formula reading(p-butylaminophenyl) should read (p-butylaminophenyl --5 line 10, thatpart of formula reading "(p-diethylaminophenyl should read(p-diethylaminophenyl)- line 1%, that part of formula reading "tolyl)"should read tolyl)- line 16, that part of formula reading 'tolyl)"should read tolyl)- --5 line 18, that part of formula reading "naphthyl)should read naphthyl)- line 36, that part of formula reading (p-dimethlaminophenyl)" should read (p-dimethylamino phenyl line Kl, that part offormula reading o-chlorophenylg" should read (ochlorophenyl)- line 6that part of formula reading "(o-chlorophenyl)" should read(o-chlorophenyl)- --5 line 73, that part of formula reading"(o-methoxycarbonylphenyl) should read (o-methoxycarbonylphenyl)- Column5, line 5, that part of formula reading (o-methoxycarbonylphenyl) shouldread (o-methoxyoarbonylphenyl)- line 9, that part of formula reading(o-ethoxycarbonylphenyl) should read (o-ethoxycarbonylphenyl)- line 11,that part of formula reading "(o-methoxycarbonylphenyl) should read(o-methoxycarbonylphenyl)- line 52, that part of formula reading(p-diethylaminophenyl)l" should read --(p-diethylaminophenyl)l--. Column6, line 22, that part of formula reading "2(2" should read --2(2--; line23, that part of formula reading "naphthyl)" should read naphthyl)- line51, that part of formula reading "bis(naph thylmethylamino) should readbis(naphthylmethylamino) Page 3 of t pages UNITED STATES PATENT ANDTRADEMARK OFFICE CERTIFICATE OF CORRECTION 4 PATENT NO. Re. 28,2 tODA-TED Reissued November 12, 197A INVENTORtK) Philip W. Jenkins It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below: line 68, thatpart of formula reading "(dimethylaniline" should read-dimethylaniline--. Column 7, line 21, "-CH-" should read -CH= Column 8,line 33, that part of formula reading "R should read --RLt-. Column 9,last line, that part of formu a reading "2,2, t,6" should read --2,t,6--. Column 12, line 22, that part of formula reading "pyridylidene)"should read pyridylidene) 5 line 26, that part of formula reading"ethylidene]" should read ethylidene]- line 35, "Photosenstive shouldread Photosensitive-. Column 15, line 38, "by a" should read by [a--;line 39, "and an" should read and] an-. Column 16, line 8, "[X]" shouldread --[X line #6, the enclosing bracket to the left of the formulashould be placed to the left of "(C)"; line 50, the enclosing bracket tothe left of the formula should be placed to the left of "(D)"; line 56,"(E)" should read -[(E)] 5 line 60, between the two formulas, -and---should be inserted; line 61, "(F)" should read -[(F)]. Column 17, line#9, "by a" should read by [a--; line 50, "and an" should read and] an-.Column 18, line 3, "c." should read e.--; line 17, "[X1" should read--[X line 53, the enclosing bracket to the left of the formula should beplaced to the left of "(C)"; line 58, the enclosing bracket to the leftof the formula should be placed to the left of "(D)"; line '71, "(F)]"should read -[(F)] Column 19, line 9, 'X' should read --X---; line 11,"R should be italicized; line 23, "20." should read --[20.-. Column 20,lines 89, "radiation." should read --radiation.]-; after Page t of tpages UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OFCORRECTION PATENT NO. :Be. 28,2 r0

DATED :Reissued November 12, 197s mvrNroRtX) :Philip w. Jenkins It iscertified that error appears in the above l'dentified patent and thatsaid Letters Patent are hereby corrected as shown below:

line 9, the following should be inserted in italics:

--2l. The element as defined in claim 2 wherein Z represents the atomsnecessary to complete a member selected from the group consisting of apyridine nucleus and a quinoline nucleus.--

Signed and Scaled this Thirty-first Day Of August 1976 [SEAL] A rresr:

RUTH C. MASON C. MARSHALL DANN Auesling Officer ('ummissr'rmvr nflarcnrsand Trademarks

2. A PHOTOSENSITIVE ELEMENT COMPRISING A SUPPORT CONTAINING ACOMPOSITION COMPRISING A. AN ESSENTIALLY COLORLESS, OXIDIZABLE,NITROGEN-CONTAINING, ORGANIC COLOR GENERATOR, WHICH WHEN CONTAINED INSAID COMPOSITION, IS STABLE TO OXIDATION BY ATMOSPHERIC OXYGEN UNDERNORMAL ROOM AND STORAGE CONDITIONS BUT WHICH IS OXIDIZABLE TO A COLOREDMATERIAL AND B. A PHOTO-OXIDANT WHICH IS CAPABLE OF OXIDIZING SAID COLORGENERATOR TO A COLORED MATERIAL WHEN SUBJECTED TO ACTINIC RADIATION,SAID PHOTO-OXIDANT HAVING A FORMULA SELECTED FROM THE GROUP CONSISTINGOF: